- Iron Complexes of Square Planar Tetradentate Polypyridyl-Type Ligands as Catalysts for Water Oxidation
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The tetradentate ligand, 2-(pyrid-2′-yl)-8-(1″,10″-phenanthrolin-2″-yl)-quinoline (ppq) embodies a quaterpyridine backbone but with the quinoline C8 providing an additional sp2 center separating the two bipyridine-like subunits. Thus, the four
- Wickramasinghe, Lanka D.,Zhou, Rongwei,Zong, Ruifa,Vo, Pascal,Gagnon, Kevin J.,Thummel, Randolph P.
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- METHODS FOR MAKING QUINOLINYLDIAMINES
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The present disclosure provides methods for making quinolinyldiamine products from quinolinyl starting materials. In addition, the quinolinyldiamines can be used as ligands or ligand precursors for catalysts, e.g. for use in olefin polymerization.
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Paragraph 283-284
(2020/03/23)
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- Fe and Co Complexes of Rigidly Planar Phosphino-Quinoline-Pyridine Ligands for Catalytic Hydrosilylation and Dehydrogenative Silylation
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Co and Fe dihalide complexes of a new rigidly planar PNN ligand platform are prepared and examined as precatalysts for hydrosilylation of alkenes. Lithiation of Thummel's 8-bromo-2-(pyrid-2′-yl)quinoline followed by treatment with (i-Pr)2PCl and (C6F5)2PCl afforded the phosphine-quinoline-pyridine ligands, abbreviated RPQpy for R = i-Pr and C6F5, respectively. These ligands form 1:1 adducts with the dichlorides and dibromides of iron and cobalt. Crystallographic characterization of FeBr2(iPrPQpy), FeBr2(ArFPQpy), CoCl2(iPrPQpy), CoBr2(iPrPQpy), and CoCl2(ArFPQpy) confirmed that the M-P-C-C-N-C-C-N portion of these complexes is planar within 0.078 ? unlike previous generations of PNN complexes where deviations from planarity were ~0.35 ?. Bond distances as well as magnetism indicate that the Fe complexes are high spin and the cobalt complexes are high spin or participate in spin equilibria. Also investigated were the NNN analogues of the RPQpy ligands, wherein the phosphine group was replaced by the mesityl ketimine. The complexes FeBr2(MesNQpy) and CoCl2(MesNQpy) were characterized crystallographically. Reduction of MX2(RPQpy) complexes with NaBHEt3 generates catalysts active for anti-Markovnikov silylation of simple and complex 1-alkenes with a variety of hydrosilanes. Catalysts derived from MesNQpy exhibited low activity. Fe-RPQpy derived catalysts favor hydrosilylation, whereas Co-RPQpy based catalysts favor dehydrogenative silylation. Catalysts derived from CoX2(iPrPQpy) convert hydrosilanes and ethylene to vinylsilanes. Related experiments were conducted on propylene to give propenylsilanes.
- Basu, Debashis,Gilbert-Wilson, Ryan,Gray, Danielle L.,Rauchfuss, Thomas B.,Dash, Aswini K.
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supporting information
p. 2760 - 2768
(2018/09/10)
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- Heterocoumarins Are Selective Carbonic Anhydrase IX and XII Inhibitors with Cytotoxic Effects against Cancer Cells Lines
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We have synthesized a new series of coumarin-based compounds demonstrating high selectivity and potent effects with low nanomolar affinity against the tumor associated carbonic anhydrase (CA, EC 4.2.1.1) isoforms hCA IX and XII. A number of these compounds were evaluated ex vivo against human prostate (PC3) and breast (MDA-MB-231) cancer cell lines. Compounds 4b and 15 revealed effective cytotoxic effects after 48 h of incubation in both normoxic and hypoxic conditions with PC3 cancer cell line. However, compound 3 showed selective cytotoxic effects against MDA-MB-231 in hypoxic condition. These results may be of particular importance for the choice of future drug candidates targeting hypoxic tumors and metastases, considering the fact that a selective carbonic anhydrase CA IX inhibitor (SLC-0111) is presently in phase II clinical trials.
- Angeli, Andrea,Trallori, Elena,Carta, Fabrizio,Di Cesare Mannelli, Lorenzo,Ghelardini, Carla,Supuran, Claudiu T.
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supporting information
p. 947 - 951
(2018/09/12)
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- Cooperative or Oxidative Hydrogen Addition to 2-Hydroxypyridonate Iridium Complexes: Dependence on Oxidation State
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Iridium(III)–pyridone complexes are commonly found to react in a cooperative and redox-neutral manner with dihydrogen and alcohols. In this work, the reactivity preferences of IrI–pyridone complexes were investigated under a variety of conditions. We have found that, in contrast to IrIII–pyridones, IrI–pyridone complexes display a strong preference to react non-cooperatively. With a new chelating 2-hydroxy-8-diphenylphosphinoquinoline ligand that does not dissociate after hydrogen addition, oxidative addition is still preferred. In the preparation of mono- and bidentate neutral and anionic pyridone ligands, Vaska's complex was used as a point of reference. We expect these findings to have implications for catalyst development in the field of metal–ligand cooperation.
- Forrest, Sebastian J. K.,Manojveer, Seetharaman,Johnson, Magnus T.
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p. 3239 - 3243
(2017/07/22)
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- Scalable and Practical Synthesis of Halo Quinolin-2(1H)-ones and Quinolines
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A practical and scalable synthesis of halo quinolin-2(1H)-ones is presented. The heterocycles are easily accessed from inexpensive halo anilines in a two-step sequence. The anilines are acylated with methyl 3,3-dimethoxypropionate under basic conditions in quantitative yields. The crude amides undergo cyclization in sulfuric acid to the desired halo quinolin-2(1H)-ones in 28-93% yield (2 steps). The synthetic sequence was successfully applied on 800 g scale. Anilines with strong electron withdrawing or electron donating groups were poor substrates for this procedure. 6-Iodoquinolin-2(1H)-one and 6-bromo-8-iodoquinolin-2(1H)-one were further functionalized to obtain quinolines substituted with various functional groups.
- Zaugg, Cornelia,Schmidt, Gunther,Abele, Stefan
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supporting information
p. 1003 - 1011
(2017/07/26)
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- Noncovalent Interactions in Ir-Catalyzed C-H Activation: L-Shaped Ligand for Para-Selective Borylation of Aromatic Esters
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An efficient strategy for the para-selective borylation of aromatic esters is described. For achieving high para-selectivity, a new catalytic system has been developed modifying the core structure of the bipyridine. It has been proposed that the L-shaped ligand is essential to recognize the functionality of the oxygen atom of the ester carbonyl group via noncovalent interaction, which provides an unprecedented controlling factor for para-selective C-H activation/borylation.
- Hoque, Md Emdadul,Bisht, Ranjana,Haldar, Chabush,Chattopadhyay, Buddhadeb
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supporting information
p. 7745 - 7748
(2017/06/21)
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- Computational and experimental evaluation of α-(N-2-quinolonyl)ketones: a new class of nonbiaryl atropisomers
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Given the usefulness of atropisomers within both asymmetric catalysis and pharmaceuticals, a thorough computational study of substituted α-(N-2-quinolonyl)ketones has been conducted. This class of tertiary amides is unique, as the amide is embedded within an aromatic construct, and the nitrogen bears an aliphatic substituent. Using a computational approach, 8′-substituted quinolones were identified as potential class 2 and 3 atropisomeric targets with calculated C–N rotational barriers of greater than 20?kcal/mol. These results, along with experimental efforts toward the synthesis of these targets, are reported.
- Bootsma, Andrea N.,Anderson, Carolyn E.
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p. 4834 - 4837
(2016/10/05)
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- Synthesis of new 1-Aryl-4-(biarylmethylene)piperazine ligands, structurally related to adoprazine (SLV313)
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A series of new 1-aryl-4-(biarylmethylene)piperazines has been synthesized. These ligands are structurally related to SLV-313, a potential atypical antipsychotic having potent D2 receptor antagonist and 5-HT 1A receptor agonist prope
- Ullah, Nisar
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scheme or table
p. 75 - 84
(2012/04/11)
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- Design, synthesis, and evaluation in vitro of quinoline-8-carboxamides, a new class of poly(adenosine-diphosphate-ribose)polymerase-1 (PARP-1) inhibitor
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Poly(ADP-ribose)polymerase-1 is an important target enzyme in drug design; inhibitors have a wide variety of therapeutic activities. A series of quinoline-8-carboxamides was designed to maintain the required pharmacophore conformation through an intramolecular hydrogen bond. 3-Substituted quinoline-8-carboxamides were synthesized by Pd-catalyzed couplings (Suzuki, Sonogashira, Stille) to 3-iodoquinoline-8-carboxamide, an efficient process that introduces diversity in the final step. 2-Substituted quinoline-8-carboxamides were prepared by selective Pd-catalyzed couplings at the 2-position of 2,8-dibromoquinoline, followed by lithium-bromine exchange of the intermediate 2-(alkyl/aryl)-8-bromoquinolines and reaction with trimethylsilyl isocyanate. The intramolecular hydrogen bond was confirmed by X-ray and by NMR. The SAR of the 3-substituted compounds for inhibition of human recombinant PARP-1 activity showed a requirement for a small narrow group. Substituents in the 2-position increased potency, with the most active 2-methylquinoline-8-carboxamide having IC50 = 500 nM (IC50 = 1.8 μM for 5-aminoisoquinolin-1- one (5-AIQ, a standard water-soluble inhibitor)).
- Lord, Anna-Marie,Mahon, Mary F.,Lloyd, Matthew D.,Threadgill, Michael D.
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supporting information; experimental part
p. 868 - 877
(2009/11/30)
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- IMIDAZO[1,2-A]PYRIDINE COMPOUNDS AS RECEPTOR TYROSINE KINASE INHIBITORS
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Compounds of Formula I: in which A, B, R1, R1a, R2, R3, R4, R5 R6, R7 and R8 have the meanings given in the specification, are receptor tyrosine inhibitors useful in the treatment of diseases mediated by class 3 and class 5 receptor tyrosine kinases. Particular compounds of this invention have also been found to be inhibitors of Pim-1.
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Page/Page column 29
(2008/12/04)
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- IMIDAZO[1,2-A]PYRIDINE COMPOUNDS AS RECEPTOR TYROSINE KINASE INHIBITORS
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Compounds of Formula (I) in which A, B, R1, R1a, R2, R3, R4, R5, R6, R7 and R8 have the meanings given in the specification, are receptor tyrosine inhibitors useful in the treatment of diseases mediated by class 3 and class 5 receptor tyrosine kinases. Particular compounds of this invention have also been found to be inhibitors of Pim-1
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Page/Page column 28
(2008/12/04)
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- Pyrrolo[3,2,1-ij]quinoline-4-one derivatives for treating tuberculosis
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Tricyclic nitrogen-containing compounds of Formula (I) and pharmaceutically acceptable derivatives thereof: compositions containing them, their use in the treatment of tuberculosis, and methods for the preparation of such compounds.
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- TRICYCLIC COMPOUNDS AS ANTIBACTERIALS
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Tricyclic nitrogen containing compounds of formula (I) and their use as antibacterials.
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- Compounds
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Tricyclic nitrogen containing compounds and their use as antibacterials
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Page/Page column 38
(2008/12/08)
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- Substituted piperazine derivatives, the preparation thereofand their use as medicaments
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The present invention relates to substituted piperazine derivatives of general formula , (I wherein Ra, Rb, Rc, Rf, Rg, X, m and n are defined as in claim 1, the isomers and salts thereof, particularly the physiologically acceptable salts thereof, which are valuable inhibitors of the microsomal triglyceride-transfer protein (MTP), medicaments containing these compounds and their use, as well as the preparation thereof.
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- Recommendable routes to trifluoromethyl-substituted pyridine- and quinolinecarboxylic acids
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As part of a case study, rational strategies for the preparation of all ten 2-, 3-, or 4-pyridinecarboxylic acids and all nine 2-, 3-, 4-, or 8-quinolinecarboxylic acids bearing trifluoromethyl substituents at the 2-, 3-, or 4-position were elaborated. The trifluoromethyl group, if not already present in the precursor, was introduced either by the deoxygenative fluorination of suitable carboxylic acids with sulfur tetrafluoride or by the displacement of ring-bound bromine or iodine by trifluoromethylcopper generated in situ. The carboxy function was produced by treatment of organolithium or organomagnesium intermediates, products of halogen/metal or hydrogen/ metal permutation, with carbon dioxide. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).
- Cottet, Fabrice,Marull, Marc,Lefebvre, Olivier,Schlosser, Manfred
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p. 1559 - 1568
(2007/10/03)
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